The conversion of carbon-hydrogen bonds, especially unactivated carbon-hydrogen bonds, into other functional groups in organic compounds has always been a difficult challenge for chemists, and few methods for doing this which are selective and/or well controlled have been developed. One of these methods is the so-called Shilov-type reaction, which classically involves the combined use of a Pt[II] compound such as PtCl.sub.2 and a Pt[IV] compound, almost always the PtCl.sub.6.sup.-2 anion, especially to create oxygen functional compounds, see for instance A. E. Shilov, et al., Coordination Chemistry Reviews, vol. 24, p. 97-143 (1977); L-C. Kao, et al., J. Chem. Soc., Chem. Commun., 1991, p. 1242-1243; A. C. Hutson, et al., J. Organometal. Chem., vol. 504, p. 69-74 (1995); G. A. Luinstra, et al., J. Organometal. Chem., vol. 504, p. 75-91 (1995); L. Wang, et al., J. Mol. Catal. A, vol. 116, p. 269-275 (1997); A. E. Shilov, Activation of Saturated Hydrocarbons by Transition Metal Complexes, D. Reidel Publishing Co., Dordrecht (1984); A. E. Shilov, et al., Chem. Rev., vol. 97, p. 2879-2932 (1997); and S. S. Stahl, et al., J. Am. Chem. Soc., vol. 118, p. 5961-5976 (1996). However, this reaction has two major disadvantages, namely it is not often as selective as desired, for example organic chlorine compounds are often generated, and the expensive Pt[IV] compound must be used in stoichiometric, not catalytic, quantities. Therefore, methods for overcoming one or both of these problems would enhance the usefulness of this reaction.
The mechanism of the Shilov-type reaction is well studied, and it is believed that the Pt[IV] compound acts as an oxidant, that is when the organic compound is functionalized with, for example, hydroxyl group, the organic compound is oxidized, and the Pt[IV] is the oxidant. It has been suggested by a number of authors, see for instance S. S. Stahl, et al., Angew. Chem. Int. Ed., vol. 37, p. 2180-2192 (1998), that the use of a cheaper oxidant would make the Shilov reaction more attractive, but such an oxidant has not been found. It has been pointed out that when Pt[IV] acts as an oxidizing agent it becomes Pt[II], which is one of the reactants. Numerous attempts have also been made to diminish the by-products associated with the Shilov reaction, especially the chlorinated organic by-products, but these attempts have been only partially successful.
N. Basickes, et al., Polyhedron, vol. 14, p. 197-202(1995) describes the synthesis of tetrahydrofuran and butanediols from 1-butanol using a platinum catalyst system. No mention is made of making 3-methyltetrahydrofuran.
M. S. Freund, et al., J. of Mol. Catal., vol. 87, p. L11-L15 (1994), use electrochemical methods to oxidize p-toluenesulfonic acid in the presence of a Pt[II] compound. J. A. Labinger, et al., Organometallics, vol. 12, p. 895-905 (1993) report on the use of phosphomolybdic acid or peroxydisulfate anion as an oxidant in the oxidation of p-toluenesulfonic acid in the presence of Pt[II]. No mention is made of hydrogen peroxide in either of these references.
What are needed are improved Shilov-type processes that do not have the disadvantages and/or deficiencies inherent in the prior art.